EP0382619A1 - Process for producing foams for cosmetical and pharmaceutical use, and foams obtained by this process - Google Patents

Process for producing foams for cosmetical and pharmaceutical use, and foams obtained by this process Download PDF

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Publication number
EP0382619A1
EP0382619A1 EP90400307A EP90400307A EP0382619A1 EP 0382619 A1 EP0382619 A1 EP 0382619A1 EP 90400307 A EP90400307 A EP 90400307A EP 90400307 A EP90400307 A EP 90400307A EP 0382619 A1 EP0382619 A1 EP 0382619A1
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Prior art keywords
niosomes
group formed
dispersion
chain
chosen
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EP90400307A
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German (de)
French (fr)
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EP0382619B1 (en
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Jacqueline Griat
Liliane Ayache
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LOreal SA
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LOreal SA
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/046Aerosols; Foams
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/14Liposomes; Vesicles
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/10Dispersions; Emulsions
    • A61K9/12Aerosols; Foams
    • A61K9/122Foams; Dry foams
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/10Dispersions; Emulsions
    • A61K9/127Liposomes
    • A61K9/1271Non-conventional liposomes, e.g. PEGylated liposomes, liposomes coated with polymers
    • A61K9/1272Non-conventional liposomes, e.g. PEGylated liposomes, liposomes coated with polymers with substantial amounts of non-phosphatidyl, i.e. non-acylglycerophosphate, surfactants as bilayer-forming substances, e.g. cationic lipids

Definitions

  • the present invention relates to a process for the manufacture of foams usable in the cosmetic and pharmaceutical fields and the foams obtained by this process.
  • the foams are generated from a liquid phase by the action of a gas.
  • the liquid product to be frothed and a pressurized propellant are introduced into an enclosure which resists pressure and which is provided with a valve and an outlet nozzle.
  • the valve is then opened so as to expel the liquid phase under the action of the pressure generated by the propellant; in the container, the propellant is liquid and it is mixed with the liquid product to be dispensed to constitute the expelled liquid phase; on arrival in the atmosphere, the propellant expands and forms a foam as soon as the product to be dispensed has foaming characteristics.
  • lipids have the property of forming, in the presence of water, mesomorphic phases, the state of organization of which is intermediate between the crystalline state and the liquid state.
  • mesomorphic phases the state of organization of which is intermediate between the crystalline state and the liquid state.
  • mesomorphic phases it has already been indicated that some can swell in aqueous solution and form, by stirring, spherules (or vesicles) dispersed in the aqueous medium, these spherules being delimited by multimolecular or bimolecular layers.
  • lipid spherules or vesicles In French patents Nos. 2,315,991 and 2,543,018, dispersions in an aqueous phase D of lipid spherules or vesicles have already been described; these vesicles are characterized by their sheet structure consisting of one or more lipid layers separated from each other by layers of aqueous phase E; they can thus be used to encapsulate water-soluble active substances, for example pharmaceutical or cosmetic, and to protect them from external conditions. If the lipid compounds used to constitute such spherules are ionic compounds, they are liposomes, and if they are nonionic compounds, they are niosomes.
  • the aim of the present invention is a process for the preparation of foams, usable in the cosmetic and pharmaceutical fields, from dispersions in water of liquids immiscible with water, in particular oils, stabilized by niosomes.
  • the present invention relates to a process for the preparation of foams which can be used in the cosmetic or pharmaceutical fields, in which a fluid cosmetic or pharmaceutical product capable of forming a fluid is loaded into a chamber which resists pressure and which is provided with a valve. foam and a pressurized propellant, then the valve is opened in order to eject the cosmetic or pharmaceutical product in foam form by expansion of the propellant, characterized in that a dispersion of pharmaceuticals is used as a component of the pharmaceutical or cosmetic product a phase immiscible with water in an aqueous phase (D), stabilized by niosomes consisting of one or more layers of nonionic lipid compounds encapsulating an aqueous phase (E), this dispersion constituting 98 to 40% by weight of the charge of the enclosure, the rest of the charge consisting of 2 to 60% by weight of propellant.
  • a dispersion of pharmaceuticals is used as a component of the pharmaceutical or cosmetic product a phase immiscible with water in an aqueous phase (D
  • the present invention also relates to the cosmetic or pharmaceutical foam obtained by this process.
  • niosomes are structures easily destabilized by low molecular weight solvents and that the dispersions stabilized by these niosomes are therefore fragile in the presence of these solvents, surprisingly neither the niosomes nor the dispersion does are destroyed by the action of the propellant.
  • the propellant can be a saturated hydrocarbon having 3 or 4 carbon atoms, such as butane, isobutane, propane, or a halogenated hydrocarbon such as those marketed under the trade name "Freons", or a mixture of these compounds.
  • the lipids used for the manufacture of niosomes are non-ionic amphiphiles of natural or synthetic origin comprising, per molecule, one or more long (s) hydrocarbon chain (s).
  • the nonionic lipid compounds used for manufacturing tion of the niosomes are chosen from the group formed by: - linear or branched polyglycerol ethers of formulas: or not is an average statistical value between 2 and 6 and R is a linear or branched aliphatic chain containing 16 to 20 carbon atoms or the hydrocarbon radical of lanolin alcohols; - linear or branched polyglycerol ethers containing two fatty chains; - esters of polyglycerol and straight chain fatty acids; - polyoxyethylenated sterols; - glycolipids of natural or synthetic origin, for example cerebrosides and ⁇ or ⁇ glucosides of fatty alcohols.
  • lipid compounds in order to modify the permeability or the surface charge of the niosomes.
  • sterols for example cholesterol and ⁇ -sitosterol
  • long-chain amines and their quaternary ammonium derivatives in particular didodecyldimethylammonium bromide, bis-hydroxyalkylamines, polyoxyethylenated fatty amines or their salts, in particular their quaternary ammonium derivatives, esters of long-chain amino alcohols as well as their salts and quaternary ammonium derivatives
  • phosphoric esters of fatty alcohols for example the sodium diketyl- or dimyristylphosphate
  • alkyl sulfates for example sodium cetylsulfate
  • ionic derivatives of sterols such as cholesterol phosphates and sulf
  • the lipid compounds forming spherules at least one lipo protide, chosen from mono or polyacylated derivatives of amino acids or polypeptides in which the acyl residue R-CO comprises a C13-C19 hydrocarbon chain, at least one of the functions which links the polypeptide chain or the amino acid residue to the lipophilic chain being an amide function.
  • the lipoprotide (s) is (or are) present at a rate of 1 to 15% by weight relative to the total weight of lipid compounds proper.
  • the lipoprotides advantageously used are palmitoyl-collagenic lipoamino acid, dipalmitoyl-ON-hydroxyprolinic acid and hydroxyproline linoleate.
  • the aqueous phase E encapsulated in the niosomes contains, for example, in dissolved form or in the form of a suspension, at least one product taken from the group formed by humectants, such as glycerin, sorbitol, pentaerythritol, inositol, pyrrolidone carboxylic acid and its salts, elastin hydrolysates; artificial browning agents, such as dihydroxyacetone, erythrulose, glyceraldehyde, alpha-dialdehydes, such as tartaric aldehyde, optionally combined with dyes; water-soluble sunscreen agents; antiperspirants; deodorants; astringents; refreshing, toning, healing, keratolytic, depilatory products; extracts of animal or plant tissue; scented waters; water-soluble dyes; anti-dandruff agents; anti-seborrheic agents; oxidants such as hydrogen per
  • the aqueous phase E encapsulated in the niosomes preferably contains at least one product taken from the group formed by vitamins, hormones, enzymes such as superoxide dismutase, vaccines , anti-inflammatory drugs such as hydrocortisone, antibiotics, bactericides, antifungals, hair loss or hair growth promoting agents and retinoids.
  • the oil used to be dispersed in the aqueous phase D is advantageously taken from the group formed by fatty acid and polyol esters, in particular liquid triglycerides, and fatty acid and branched alcohol esters of formula R4 -COOR5, in which R4 represents the residue of a higher fatty acid comprising from 8 to 20 carbon atoms and R5 represents a branched hydrocarbon chain containing from 3 to 20 carbon atoms.
  • the oil is a fatty acid and polyol ester, it is preferred that it be chosen from the group formed by sunflower, corn, soybean, squash, grapeseed, sesame, macadamia, borage, black currant, and glycerol tricaprocaprylate; if the oil is an ester of higher fatty acid and branched alcohol, it is preferred that it is Purcellin oil; other vegetable oils can be used such as, for example, jojoba oil.
  • the water-immiscible liquid can also be: - a hydrocarbon, such as hexadecane, paraffin oil or perhydrosqualene; - a halogenated hydrocarbon, such as perfluorodecahydronaphthalene; - a polysiloxane; - an ester of organic acid; - an ether or a polyether; - or perfluorotributylamine.
  • the aqueous phase D which surrounds the niosomes, contains at least one adjuvant taken from the group formed by opacifiers, gelling agents, flavors, water-soluble sun filters and dyes.
  • the adjuvants which are liposoluble, can be dissolved in the water-immiscible oil dispersed in the aqueous phase D. If this water-immiscible liquid must contain dissolved adjuvants, the dissolution of these adjuvants is , preferably, carried out before carrying out the dispersion.
  • Such adjuvants can be, for example, fat-soluble sunscreens, such as 2-ethylhexyl paradimethylaminobenzoate, these perfumes or substances intended to improve the condition of dry or senile skin, in particular unsaponifiables such as unsaponifiables of soya, avocado, tocopherols , vitamins E, F, antioxidants.
  • fat-soluble sunscreens such as 2-ethylhexyl paradimethylaminobenzoate
  • these perfumes or substances intended to improve the condition of dry or senile skin in particular unsaponifiables such as unsaponifiables of soya, avocado, tocopherols , vitamins E, F, antioxidants.
  • the non-liposoluble additives are generally added to the preparation after the oil has dispersed.
  • the gelling agent can be introduced at a concentration varying between 0.1 and 2%, these percentages being expressed by weight relative to the total weight of the composition.
  • cellulose derivatives such as hydroxyethylcellulose
  • algae derivatives such as that sold under the trade name "Satiagum”
  • natural gums such as tragacanth.
  • gelling agent hydroxyethylcellulose, a mixture of carboxyvinyl acids commercially available under the name "CARBOPOL 940", the product sold under the trade name "Satiagum” or alternatively the tragacanth.
  • the aqueous phase D of dispersion of the niosomes and / or the internal aqueous phase E of the niosomes may also contain in solution a water-soluble polyamide polymer having a molecular weight of between 1,000 and 200,000, the concentration of which is from 0.01 to 5% by weight relative to the total weight of the composition.
  • polyamide polymer mention may be made of polyacrylamide, poly-beta-alanine, poly (glutamic acid), polytyrosine, polylysine, and poly (aspartic acid) and proteins such as alpha-lactalbumin, serum albumin , lactic hydrolysates, collagen hydrolysates and gelatin hydrolysates.
  • a first dispersion A is prepared, consisting of an oil dispersion in a phase aqueous, said dispersion being stabilized by niosomes.
  • a dispersion of niosomes having an average diameter of 10,000 ⁇ is obtained.
  • a second dispersion B is prepared according to the same process from the following formulation:
  • dispersions A or B prepared as above indicated as a filler in a pressurized container with one of the following four propellants: Name of the Propellant Composition of the propellant mixture P1 Butane / Propane / Isobutane (25/20/55) P2 Difluoro-dichloromethane P3 Difluoro-dichloro-methane / Dichloro-tetrafluoroethane (50/50) P4 P1 / Dichlorotetrafluoroethane (30/70)
  • Example number Propellant Dispersion Nature Quantity Nature Quantity 1 P1 30 AT 70 2 P2 30 AT 70 3 P1 30 B 70 4 P3 30 B 70 5 P4 30 B 70 these quantities are given in% by weight relative to the total load.
  • the foams obtained contain niosomes, which have therefore remained in the presence of the propellant and continue to have in the foams their action of stabilizing dispersions.
  • a charge was prepared containing 98% by weight of dispersion A and 2% of a propellant consisting of a mixture of propane, isobutane, n-butane (10/50/40).
  • the charge was kept at room temperature for 6 months and the presence of niosomes was verified by ultrastructural examination by electron microscopy using the cryofracture technique. It has been found that the charge contains niosomes having diameters between 80 and 300 nm.
  • Example 4 The charges of Examples 4 and 5 were stored for 8 months and the presence of niosomes was verified by the method described in Example 6. The presence of numerous niosomes having a diameter between 50 and 200 nm was observed in the case of the charge of Example 4 and niosomes having a diameter between 150 and 400 nm in the case of the charge of Example 5.
  • a charge was prepared containing by weight 70% of dispersion B and 30% of a propellant consisting of a butane-propane-isobutane-pentane mixture (68.2 / 8/22 / 1.8). This charge was stored for 8 months at room temperature and the presence of niosomes was verified by the method described in Example 6. A large number of niosomes having a diameter between 200 and 300 nm were observed. .

Abstract

The invention relates to a process for the preparation of cosmetics or pharmaceutical foam by foaming with the aid of a propellant. According to the invention, a charge consisting of a cosmetics or pharmaceutical product comprising a dispersion of a water-immiscible product in an aqueous solution, the said dispersion being stabilized by niosomes consisting of one or more nonionic lipid layers encapsulating an aqueous phase, the charge comprising 40 to 95% by weight of dispersion and 5 to 60% by weight of propellant, the proportions being stated with respect to the weight of the total charge of the chamber, are introduced into a chamber which is under pressure and fitted with a valve.

Description

La présente invention concerne un procédé de fabrication de mousses utilisables dans les domaines cosmétique et pharmaceutique et les mousses obtenues par ce procédé.The present invention relates to a process for the manufacture of foams usable in the cosmetic and pharmaceutical fields and the foams obtained by this process.

Dans de nombreux cas, il est avantageux dans le domaine cosmétique ou pharmaceutique d'uti­liser des produits sous forme de mousse. Ils sont généralement plus faciles à appliquer car ils sont moins denses et s'étalent plus facilement.In many cases, it is advantageous in the cosmetic or pharmaceutical field to use products in the form of foam. They are generally easier to apply because they are less dense and spread more easily.

De façon générale, les mousses sont générées à partir d'une phase liquide par action d'un gaz. On introduit, dans une enceinte, qui résiste à la pression et qui est munie d'une valve et d'un ajutage de sortie, le produit liquide à faire mousser et un propulseur pressurisé. On ouvre ensuite la valve de façon à faire expulser la phase liquide sous l'action de la pression générée par le propulseur ; dans le récipient, le propulseur est liquide et il est mélan­gé au produit liquide à distribuer pour constituer la phase liquide expulsée ; à l'arrivée dans l'atmos­phère, le propulseur se détend et forme une mousse dès lors que le produit à distribuer a des caractéristiques moussantes.Generally, the foams are generated from a liquid phase by the action of a gas. The liquid product to be frothed and a pressurized propellant are introduced into an enclosure which resists pressure and which is provided with a valve and an outlet nozzle. The valve is then opened so as to expel the liquid phase under the action of the pressure generated by the propellant; in the container, the propellant is liquid and it is mixed with the liquid product to be dispensed to constitute the expelled liquid phase; on arrival in the atmosphere, the propellant expands and forms a foam as soon as the product to be dispensed has foaming characteristics.

Par ailleurs, on sait que certains lipides possèdent la propriété de former, en présence d'eau, des phases mésomorphes, dont l'état d'organisation est intermédiaire entre l'état cristallin et l'état liquide. Parmi les lipides,qui donnent naissance à des phases mésomorphes, il a déjà été indiqué que certains peuvent gonfler en solution aqueuse et former, par agitation, des sphérules (ou vésicules) dispersées dans le milieu aqueux, ces sphérules étant délimitées par des couches multimoléculaires ou bi­moléculaires.Furthermore, it is known that certain lipids have the property of forming, in the presence of water, mesomorphic phases, the state of organization of which is intermediate between the crystalline state and the liquid state. Among the lipids, which give rise to mesomorphic phases, it has already been indicated that some can swell in aqueous solution and form, by stirring, spherules (or vesicles) dispersed in the aqueous medium, these spherules being delimited by multimolecular or bimolecular layers.

Dans les brevets français n° 2 315 991 et 2 543 018, on a déjà décrit des dispersions dans une phase aqueuse D de sphérules ou vésicules lipi­diques ; ces vésicules sont caracté­risées par leur structure en feuillets constituée d'une ou plusieurs couches lipidiques séparées les unes des autres par des couches de phase aqueuse E ; elles peuvent ainsi servir à encapsuler des substances actives hydrosolubles, par exemple pharmaceutiques ou cosmétiques, et à les protéger des conditions extérieures. Si les composés lipidiques utilisés pour constituer de telles sphérules sont des composés ioniques, il s'agit de liposomes, et s'ils sont des composés non-ioniques, il s'agit de niosomes.In French patents Nos. 2,315,991 and 2,543,018, dispersions in an aqueous phase D of lipid spherules or vesicles have already been described; these vesicles are characterized by their sheet structure consisting of one or more lipid layers separated from each other by layers of aqueous phase E; they can thus be used to encapsulate water-soluble active substances, for example pharmaceutical or cosmetic, and to protect them from external conditions. If the lipid compounds used to constitute such spherules are ionic compounds, they are liposomes, and if they are nonionic compounds, they are niosomes.

Dans les brevets français 2 485 921 et 2 490 504, on a décrit le fait que la présence de niosomes permet de stabiliser des dispersions en phase aqueuse de liquides non-miscibles à l'eau, en particulier d'huile, sans qu'il soit nécessaire d'ajouter un agent émulsifiant.In French patents 2,485,921 and 2,490,504, it has been described that the presence of niosomes makes it possible to stabilize dispersions in aqueous phase of liquids immiscible with water, in particular oil, without it it is necessary to add an emulsifying agent.

Dans les documents WO 86/01714 et EP-A-0 190 926 sont décrits des procédés de prépa­ration de liposomes par pulvérisation de la phase lipidique sous l'action d'un agent propulseur. Dans WO 86/01714 la phase lipidique pulvérisée est amenée en contact avec la surface d'une phase aqueuse pour provoquer la formation des liposomes. Dans EP-A-0 190 926 on pulvérise la phase lipidique en solution dans un solvant organique combiné avec de l'eau, par exemple sous forme d'émulsion.In documents WO 86/01714 and EP-A-0 190 926 are described methods for preparing liposomes by spraying the lipid phase under the action of a propellant. In WO 86/01714 the pulverized lipid phase is brought into contact with the surface of an aqueous phase to cause the formation of liposomes. In EP-A-0 190 926 the lipid phase is sprayed in solution in an organic solvent combined with water, for example in the form of an emulsion.

La présente invention a pour but un procédé de préparation de mousses, utilisables dans les domaines cosmétique et pharmaceutique, à partir de dispersions dans l'eau de liquides non-miscibles à l'eau, en particulier d'huiles, stabilisées par des niosomes.The aim of the present invention is a process for the preparation of foams, usable in the cosmetic and pharmaceutical fields, from dispersions in water of liquids immiscible with water, in particular oils, stabilized by niosomes.

La présente invention concerne un procédé de préparation de mousses utilisables dans les do­maines cosmétique ou pharmaceutique, dans lequel on charge, dans une enceinte qui résiste à la pression et qui est munie d'une valve, un produit cosmétique ou pharmaceutique fluide susceptible de former une mousse et un propulseur pressurisé, puis on ouvre la valve pour éjecter par détente du propulseur le produit cosmétique ou pharmaceutique sous forme de mousse, caractérisé par le fait que l'on utilise, en tant que composant du produit pharmaceutique ou cosmétique, une dispersion d'une phase non-­miscible à l'eau dans une phase aqueuse (D), sta­bilisée par des niosomes constitués d'une ou plusieurs couches de composés lipidiques non-ioniques encapsulant une phase aqueuse (E), cette dispersion constituant 98 à 40% en poids de la charge de l'enceinte, le reste de la charge étant constitué de 2 à 60% en poids de propulseur.The present invention relates to a process for the preparation of foams which can be used in the cosmetic or pharmaceutical fields, in which a fluid cosmetic or pharmaceutical product capable of forming a fluid is loaded into a chamber which resists pressure and which is provided with a valve. foam and a pressurized propellant, then the valve is opened in order to eject the cosmetic or pharmaceutical product in foam form by expansion of the propellant, characterized in that a dispersion of pharmaceuticals is used as a component of the pharmaceutical or cosmetic product a phase immiscible with water in an aqueous phase (D), stabilized by niosomes consisting of one or more layers of nonionic lipid compounds encapsulating an aqueous phase (E), this dispersion constituting 98 to 40% by weight of the charge of the enclosure, the rest of the charge consisting of 2 to 60% by weight of propellant.

La présente invention concerne également la mousse cosmétique ou pharmaceutique obtenue par ce procédé.The present invention also relates to the cosmetic or pharmaceutical foam obtained by this process.

La demanderesse a découvert que, bien que les niosomes soient des structures facilement déstabi­lisées par des solvants de bas poids moléculaire et que les dispersions stabilisées par ces niosomes soient donc fragiles en présence de ces solvants, de façon surprenante ni les niosomes, ni la dispersion ne sont détruits par action du propulseur.The Applicant has discovered that, although the niosomes are structures easily destabilized by low molecular weight solvents and that the dispersions stabilized by these niosomes are therefore fragile in the presence of these solvents, surprisingly neither the niosomes nor the dispersion does are destroyed by the action of the propellant.

Selon l'invention, le propulseur peut être un hydrocarbure saturé ayant 3 ou 4 atomes de carbone, tel que le butane, l'isobutane, le propane, ou un hydrocarbure halogéné tels que ceux commercialisés sous la dénomination commerciale "Fréons", ou un mélange de ces composés.According to the invention, the propellant can be a saturated hydrocarbon having 3 or 4 carbon atoms, such as butane, isobutane, propane, or a halogenated hydrocarbon such as those marketed under the trade name "Freons", or a mixture of these compounds.

Les lipides utilisés pour la fabrication des niosomes sont des amphiphiles non-ioniques d'origine naturelle ou synthétique comportant, par molécule,une ou plusieurs longue(s) chaîne(s) hydrocarbonée(s). Avantageusement, les composés lipidiques non-ioniques utilisés pour la fabrica­ tion des niosomes sont choisis dans le groupe formé par :
- les éthers de polyglycérol linéaires ou ramifiés de formules :

Figure imgb0001
n est une valeur statistique moyenne compri­se entre 2 et 6 et R est une chaîne aliphatique linéaire ou ramifiée contenant 16 à 20 atomes de carbone ou le radical hydrocarboné des alcools de lanoline ;
- les éthers de polyglycérol linéaires ou ramifiés contenant deux chaînes grasses ;
- les esters de polyglycérol et d'acides gras à chaîne linéaire ;
- les stérols polyoxyéthylénés ;
- les glycolipides d'origine naturelle ou synthétique, par exemple les cérébrosides et les α ou β glucosides d'alcools gras.The lipids used for the manufacture of niosomes are non-ionic amphiphiles of natural or synthetic origin comprising, per molecule, one or more long (s) hydrocarbon chain (s). Advantageously, the nonionic lipid compounds used for manufacturing tion of the niosomes are chosen from the group formed by:
- linear or branched polyglycerol ethers of formulas:
Figure imgb0001
or not is an average statistical value between 2 and 6 and R is a linear or branched aliphatic chain containing 16 to 20 carbon atoms or the hydrocarbon radical of lanolin alcohols;
- linear or branched polyglycerol ethers containing two fatty chains;
- esters of polyglycerol and straight chain fatty acids;
- polyoxyethylenated sterols;
- glycolipids of natural or synthetic origin, for example cerebrosides and α or β glucosides of fatty alcohols.

De façon connue, divers autres additifs peuvent être as­sociés aux composés lipidiques en vue de modifier la perméabilité ou la charge superficielle des niosomes. On citera, à cet égard, l'ad­dition éventuelle des alcools et diols à longue chaîne, des stérols, par exemple le cholestérol et le β-sitostérol, des amines à longue chaîne et leurs dérivés ammonium quaternaires, en particulier le bromure de didodécyldiméthylammonium, des bis-hydroxyalkylamines, des amines grasses polyoxyéthylénées ou leurs sels, en particulier leurs dérivés ammonium quaternaires, des esters d'amino-alcools à longue chaîne ainsi que leurs sels et dérivés ammonium quaternaires, des esters phosphoriques d'alcools gras, par exemple le dicétyl- ou le dimyristyl- phosphate de sodium, des alcoylsulfates, par exem­ple le cétylsulfate de sodium, et des dérivés ioniques des stérols, tels que les phosphates et sulfates de cholestérol.In known manner, various other additives can be combined with the lipid compounds in order to modify the permeability or the surface charge of the niosomes. In this regard, mention may be made of the possible addition of long-chain alcohols and diols, sterols, for example cholesterol and β-sitosterol, long-chain amines and their quaternary ammonium derivatives, in particular didodecyldimethylammonium bromide, bis-hydroxyalkylamines, polyoxyethylenated fatty amines or their salts, in particular their quaternary ammonium derivatives, esters of long-chain amino alcohols as well as their salts and quaternary ammonium derivatives, phosphoric esters of fatty alcohols, for example the sodium diketyl- or dimyristylphosphate, alkyl sulfates, for example sodium cetylsulfate, and ionic derivatives of sterols, such as cholesterol phosphates and sulfates.

On peut également ajouter aux composés lipidiques formant des sphérules au moins un lipo­ protide, choisi parmi les dérivés mono ou polyacylés d'aminoacides ou de polypeptides dans lesquels le reste acyle R-CO comporte une chaîne hydrocarbonée en C₁₃-C₁₉, au moins une des fonctions qui relie la chaîne polypeptidique ou le reste d'aminoacide à la chaîne lipophile étant une fonction amide. Le (ou les) lipoprotide(s) est (ou sont) présent(s) à raison de 1 à 15% en poids par rapport au poids total de composés lipidiques proprement dits. Les lipoprotides avantageusement utilisés sont le lipoaminoacide palmitoyl-collagénique, l'acide dipalmitoyl-O-N-hydroxyprolinique et le linoléate d'hydroxyproline.It is also possible to add to the lipid compounds forming spherules at least one lipo protide, chosen from mono or polyacylated derivatives of amino acids or polypeptides in which the acyl residue R-CO comprises a C₁₃-C₁₉ hydrocarbon chain, at least one of the functions which links the polypeptide chain or the amino acid residue to the lipophilic chain being an amide function. The lipoprotide (s) is (or are) present at a rate of 1 to 15% by weight relative to the total weight of lipid compounds proper. The lipoprotides advantageously used are palmitoyl-collagenic lipoamino acid, dipalmitoyl-ON-hydroxyprolinic acid and hydroxyproline linoleate.

Avantageusement, on peut utiliser, pour constituer la dispersion de niosomes, de 0,5 à 25% en poids d'amphiphile(s) non-ionique(s) par rapport au poids total de la dispersion de nioso­mes à obtenir.Advantageously, it is possible to use, to constitute the dispersion of niosomes, from 0.5 to 25% by weight of non-ionic amphiphile (s) relative to the total weight of the dispersion of niosomes to be obtained.

Les niosomes utilisés sont, de préférence, des sphérules ayant un diamètre moyen compris entre 100 et 50.000 Å telles que celles décrites dans le brevet français 2 315 991.The niosomes used are preferably spherules having an average diameter of between 100 and 50,000 Å such as those described in French patent 2,315,991.

On peut prévoir que la phase aqueuse E encapsulée dans les niosomes soit une solution aqueuse de substance cosmétique ou pharmaceutique active, de préférence isoosmotique par rapport à la phase D de la dispersion.Provision may be made for the aqueous phase E encapsulated in the niosomes to be an aqueous solution of active cosmetic or pharmaceutical substance, preferably isoosmotic with respect to phase D of the dispersion.

Pour une composition cosmétique, la phase aqueuse E encapsulée dans les niosomes contient par exemple, sous forme dissoute ou sous forme de suspension, au moins un produit pris dans le groupe formé par les humectants, tels que la glycérine, le sorbitol, le pentaérythritol, l'inositol, l'acide pyrrolidone-carboxylique et ses sels, les hydrolysats d'élastine ; les agents de brunissage artificiel, tels que la dihydroxy-acétone, l'érythrulose, le glycéraldéhyde, les alpha-dialdéhydes, tels que l'aldéhyde tartrique, éventuellement associés à des colorants ; les agents anti-solaires hydroso­lubles ; les anti-perspirants ; les déodorants ; les astringents ; les produits rafraîchissants, toniques, cicatrisants, kératolytiques, dépilatoires ; les extraits de tissus animaux ou végétaux ; les eaux parfumées ; les colorants hydrosolubles ; les agents anti-pelliculaires ; les agents anti-­séborrhéiques ; les oxydants tels que l'eau oxygénée et les réducteurs tels que l'acide thioglycolique et ses sels.For a cosmetic composition, the aqueous phase E encapsulated in the niosomes contains, for example, in dissolved form or in the form of a suspension, at least one product taken from the group formed by humectants, such as glycerin, sorbitol, pentaerythritol, inositol, pyrrolidone carboxylic acid and its salts, elastin hydrolysates; artificial browning agents, such as dihydroxyacetone, erythrulose, glyceraldehyde, alpha-dialdehydes, such as tartaric aldehyde, optionally combined with dyes; water-soluble sunscreen agents; antiperspirants; deodorants; astringents; refreshing, toning, healing, keratolytic, depilatory products; extracts of animal or plant tissue; scented waters; water-soluble dyes; anti-dandruff agents; anti-seborrheic agents; oxidants such as hydrogen peroxide and reducing agents such as thioglycolic acid and its salts.

Dans le cas d'une composition utilisable en pharmacie, la phase aqueuse E encapsulée dans les niosomes contient, de préférence, au moins un produit pris dans le groupe formé par les vitamines, les hormones, les enzymes tels que la superoxyde dismutase, les vaccins, les anti-inflammatoires tels que l'hydrocortisone, les antibiotiques, les bactéricides, les antifongiques, les agents antichute ou favorisant la repousse des cheveux et les rétinoïdes.In the case of a composition which can be used in pharmacies, the aqueous phase E encapsulated in the niosomes preferably contains at least one product taken from the group formed by vitamins, hormones, enzymes such as superoxide dismutase, vaccines , anti-inflammatory drugs such as hydrocortisone, antibiotics, bactericides, antifungals, hair loss or hair growth promoting agents and retinoids.

Dans la composition selon l'invention, la phase aqueuse D entourant les niosomes contient sous forme de dispersion au moins une phase liquide non-miscible à l'eau. Cette phase liquide non-­miscible à l'eau est, de préférence, une huile.In the composition according to the invention, the aqueous phase D surrounding the niosomes contains in the form of a dispersion at least one liquid phase immiscible with water. This water-immiscible liquid phase is preferably an oil.

L'huile utilisée pour être dispersée dans la phase aqueuse D est avantageusement prise dans le groupe formé par les esters d'acide gras et de polyol, notamment les triglycérides liquides, et les esters d'acide gras et d'alcool ramifié de formule R₄-COOR₅, dans laquelle R₄ représente le reste d'un acide gras supérieur comportant de 8 à 20 atomes de carbone et R₅ représente une chaîne hydrocarbonée ramifiée contenant de 3 à 20 atomes de carbone. Si l'huile est un ester d'acide gras et de polyol, on préfère qu'elle soit choisie dans le groupe formé par les huiles de tournesol, de maïs, de soja, de courge, de pépins de raisin, de sésame, de macadamia, de bourrache, de cassis, et le tricaprocaprylate de glycérol ; si l'huile est un ester d'acide gras supérieur et d'alcool ramifié, on préfère que ce soit l'huile de Purcellin ; d'autres huiles végétales peuvent être utilisées comme, par exemple, l'huile de jojoba.The oil used to be dispersed in the aqueous phase D is advantageously taken from the group formed by fatty acid and polyol esters, in particular liquid triglycerides, and fatty acid and branched alcohol esters of formula R₄ -COOR₅, in which R₄ represents the residue of a higher fatty acid comprising from 8 to 20 carbon atoms and R₅ represents a branched hydrocarbon chain containing from 3 to 20 carbon atoms. If the oil is a fatty acid and polyol ester, it is preferred that it be chosen from the group formed by sunflower, corn, soybean, squash, grapeseed, sesame, macadamia, borage, black currant, and glycerol tricaprocaprylate; if the oil is an ester of higher fatty acid and branched alcohol, it is preferred that it is Purcellin oil; other vegetable oils can be used such as, for example, jojoba oil.

Le liquide non-miscible à l'eau peut égale­ment être :
- un hydrocarbure, tel que l'hexadécane, l'huile de paraffine ou le perhydrosqualène ;
- un hydrocarbure halogéné, tel que le perfluorodécahydronaphtalène ;
- un polysiloxane ;
- un ester d'acide organique ;
- un éther ou un polyéther ;
- ou la perfluorotributylamine.
The water-immiscible liquid can also be:
- a hydrocarbon, such as hexadecane, paraffin oil or perhydrosqualene;
- a halogenated hydrocarbon, such as perfluorodecahydronaphthalene;
- a polysiloxane;
- an ester of organic acid;
- an ether or a polyether;
- or perfluorotributylamine.

On peut également prévoir que la phase aqueuse D, qui entoure les niosomes, contienne au moins un adjuvant pris dans le groupe formé par les opacifiants, les gélifiants, les arômes, les filtres solaires hydrosolubles et les colorants. Les adjuvants, qui sont liposolubles, peuvent être dissous dans l'huile non-miscible à l'eau dispersée dans la phase aqueuse D. Si ce liquide non-miscible à l'eau doit contenir des adjuvants dissous, la dis­solution de ces adjuvants est, de préférence, réalisée avant d'effectuer la dispersion.It is also possible to provide that the aqueous phase D, which surrounds the niosomes, contains at least one adjuvant taken from the group formed by opacifiers, gelling agents, flavors, water-soluble sun filters and dyes. The adjuvants, which are liposoluble, can be dissolved in the water-immiscible oil dispersed in the aqueous phase D. If this water-immiscible liquid must contain dissolved adjuvants, the dissolution of these adjuvants is , preferably, carried out before carrying out the dispersion.

De tels adjuvants peuvent être, par exemple, des filtres solaires liposolubles, tels que le paradiméthylamino­benzoate de 2-éthyl-hexyle, ces parfums ou des substances destinées à améliorer l'état des peaux sèches ou séniles, en particulier des insaponifiables tels que des insaponifiables de soja, d'avocat, des tocophérols, des vitamines E, F, des anti-oxydants.Such adjuvants can be, for example, fat-soluble sunscreens, such as 2-ethylhexyl paradimethylaminobenzoate, these perfumes or substances intended to improve the condition of dry or senile skin, in particular unsaponifiables such as unsaponifiables of soya, avocado, tocopherols , vitamins E, F, antioxidants.

Les additifs non-liposolubles sont généra­lement ajoutés à la préparation après la dispersion de l'huile. Le gélifiant peut être introduit à une concentration variant entre 0,1 et 2%, ces pourcentages etant exprimés en poids par rapport au poids total de la composition. Parmi les gélifiants utilisables, on peut citer les dérivés de cellulose, tels que l'hydroxyéthylcellulose ; des dérivés d'algues, tels que celui vendu sous le nom commercial "Satiagum" ; ou encore des gommes naturelles, telles que l'adragante. On préfère utiliser, à titre de gélifiant, l'hydroxyéthylcellulose, un mélange d'acides carboxyvinyliques disponibles dans le commerce sous le nom de "CARBOPOL 940", le produit vendu sous le nom com­mercial "Satiagum" ou encore de l'adragante.The non-liposoluble additives are generally added to the preparation after the oil has dispersed. The gelling agent can be introduced at a concentration varying between 0.1 and 2%, these percentages being expressed by weight relative to the total weight of the composition. Among the gelling agents which can be used, mention may be made of cellulose derivatives, such as hydroxyethylcellulose; algae derivatives, such as that sold under the trade name "Satiagum"; or natural gums, such as tragacanth. It is preferred to use, as gelling agent, hydroxyethylcellulose, a mixture of carboxyvinyl acids commercially available under the name "CARBOPOL 940", the product sold under the trade name "Satiagum" or alternatively the tragacanth.

La phase aqueuse D de dispersion des niosomes et/ou la phase aqueuse interne E des niosomes peut également contenir en solution un polymère polyamide hydrosoluble ayant un poids moléculaire compris entre 1.000 et 200.000, dont la concentration est de 0,01 à 5% en poids par rapport au poids total de la composition. Comme polymère polyamide, on peut citer le polyacrylamide, la poly-bêta-alanine, le poly(acide glutamique), la polytyrosine, la polylysine, et le poly(acide aspartique) et des protéines telles que l'alpha-lactalbumine, le sérum­albumine, les hydrolysats lactiques, les hydro­lysats de collagène et les hydrolysats de gélatine.The aqueous phase D of dispersion of the niosomes and / or the internal aqueous phase E of the niosomes may also contain in solution a water-soluble polyamide polymer having a molecular weight of between 1,000 and 200,000, the concentration of which is from 0.01 to 5% by weight relative to the total weight of the composition. As polyamide polymer, mention may be made of polyacrylamide, poly-beta-alanine, poly (glutamic acid), polytyrosine, polylysine, and poly (aspartic acid) and proteins such as alpha-lactalbumin, serum albumin , lactic hydrolysates, collagen hydrolysates and gelatin hydrolysates.

Pour réaliser la dispersion dans la phase aqueuse D des sphérules lipidiques, on peut utiliser n'importe lequel des procédés antérieurement connus et décrits.To carry out the dispersion in the aqueous phase D of the lipid spherules, any of the methods previously known and described can be used.

On peut, par exemple, utiliser le procédé, qui consiste à dissoudre les lipides dans un solvant volatil, à former un film mince de lipides sur les parois d'un flacon par évaporation du solvant, à introduire dans ledit flacon la phase aqueuse E à encapsuler et à agiter le mélange mécaniquement jusqu'à l'obtention de la dispersion de sphérules à la taille désirée ; dans ce cas, les phases aqueuses D et E sont nécessairement identiques.One can, for example, use the method which consists in dissolving the lipids in a volatile solvent, in forming a thin film of lipids on the walls of a bottle by evaporation of the solvent, in introducing into said bottle the aqueous phase E to encapsulate and stir the mixture mechanically until the dispersion of spherules of the desired size is obtained; in this case, the aqueous phases D and E are necessarily identical.

On peut aussi utiliser le procédé décrit dans le brevet français n° 2 315 991. Ce procédé convient particulièrement bien, lorsque l'on souhaite utiliser des sphérules multilamellaires.It is also possible to use the method described in French patent no. 2 315 991. This method is particularly suitable when it is desired to use multilamellar spherules.

Dans le cas où l'on désire des sphérules unilamellaires, on peut utiliser, pour leur prépa­ration, le procédé décrit dans le brevet français n° 2 543 018.If unilamellar spherules are desired, the process described in French Patent No. 2,543,018 can be used for their preparation.

Les exemples donnés ci-dessous, à titre purement illustratifs et non limitatifs, permettront de mieux comprendre l'invention.The examples given below, purely by way of non-limiting illustration, will allow a better understanding of the invention.

PREPARATION D'UNE DISPERSION APREPARATION OF A DISPERSION A

On prépare une première dispersion A cons­tituée par une dispersion d'huile dans une phase aqueuse, ladite dispersion étant stabilisée par des niosomes.A first dispersion A is prepared, consisting of an oil dispersion in a phase aqueous, said dispersion being stabilized by niosomes.

1ère phase :1st phase:

On utilise le procédé décrit dans le brevet français n° 2 315 991 pour obtenir une dis­persion de niosomes dans une phase aqueuse à partir de la formulation suivante :

Figure imgb0002
The process described in French patent No. 2 315 991 is used to obtain a dispersion of niosomes in an aqueous phase from the following formulation:
Figure imgb0002

On obtient une dispersion de niosomes ayant un diamètre moyen de 10.000 Å.A dispersion of niosomes having an average diameter of 10,000 Å is obtained.

2ème phase :2nd phase:

On ajoute au mélange ainsi obtenu 15 g d'huile de sésame et 0,4 g de parfum. On soumet le tout à une agitation mécanique jusqu'à obtention d'une dis­persion homogène très fine.15 g of sesame oil and 0.4 g of perfume are added to the mixture thus obtained. The whole is subjected to mechanical stirring until a very fine homogeneous dispersion is obtained.

On ajoute enfin les substances suivantes : - Acide polyvinylcarboxylique commercialisé sous le nom de "CARBOPOL 940"... 0,4 g - Triéthanolamine... 0,4 g - Eau déminéralisée... 37,0 g Finally, the following substances are added: - Polyvinylcarboxylic acid marketed under the name of "CARBOPOL 940" ... 0.4 g - Triethanolamine ... 0.4 g - Demineralized Water... 37.0 g

PREPARATION D'UNE DISPERSION BPREPARATION OF A DISPERSION B

On prépare selon le même procédé une seconde dispersion B à partir de la formulation suivante :

Figure imgb0003
A second dispersion B is prepared according to the same process from the following formulation:
Figure imgb0003

On soumet le tout à une agitation mécanique jusqu'à obtention d'une dispersion homogène très fine.The whole is subjected to mechanical stirring until a very fine homogeneous dispersion is obtained.

On ajoute enfin à la dispersion les subs­tances suivantes : - Acide polyvinylcarboxylique commercialisé sous le nom de "CARBOPOL 940"... 0,4 g - Triéthanolamine... 0,4 g - Eau déminéralisée... 39,6 g Finally, the following substances are added to the dispersion: - Polyvinylcarboxylic acid marketed under the name of "CARBOPOL 940" ... 0.4 g - Triethanolamine ... 0.4 g - Demineralized Water... 39.6g

EXEMPLES 1 à 5 :EXAMPLES 1 to 5:

On a introduit les dispersions A ou B préparées comme ci-dessus indiqué comme charge dans un récipient pressurisé avec l'un des quatre gaz propul­seurs suivants : Dénomination du Propulseur Composition du mélange formant le propulseur P₁ Butane/Propane/Isobutane (25/20/55) P₂ Difluoro-dichloro-méthane P₃ Difluoro-dichloro-méthane/Dichloro-tétrafluoroéthane (50/50) P₄ P₁/Dichlorotétrafluoroéthane (30/70) We introduced dispersions A or B prepared as above indicated as a filler in a pressurized container with one of the following four propellants: Name of the Propellant Composition of the propellant mixture P₁ Butane / Propane / Isobutane (25/20/55) P₂ Difluoro-dichloromethane P₃ Difluoro-dichloro-methane / Dichloro-tetrafluoroethane (50/50) P₄ P₁ / Dichlorotetrafluoroethane (30/70)

On réalise les cinq exemples suivants correspon­dant à la mise en oeuvre du procédé selon l'invention : N° de l'exemple Propulseur Dispersion Nature Quantité Nature Quantité 1 P₁ 30 A 70 2 P₂ 30 A 70 3 P₁ 30 B 70 4 P₃ 30 B 70 5 P₄ 30 B 70 ces quantités sont données en % en poids par rapport à la charge totale. The following five examples are carried out corresponding to the implementation of the method according to the invention: Example number Propellant Dispersion Nature Quantity Nature Quantity 1 P₁ 30 AT 70 2 P₂ 30 AT 70 3 P₁ 30 B 70 4 P₃ 30 B 70 5 P₄ 30 B 70 these quantities are given in% by weight relative to the total load.

On constate que, dans tous les cas, les mousses obtenues contiennent des niosomes, qui ont donc subsisté en présence du propulseur et continuent d'avoir dans les mousses leur action de stabilisation des dispersions.It is noted that, in all cases, the foams obtained contain niosomes, which have therefore remained in the presence of the propellant and continue to have in the foams their action of stabilizing dispersions.

EXEMPLE 6EXAMPLE 6

On a préparé une charge contenant en poids 98 % de la dispersion A et 2 % d'un propulseur constitué d'un mélange propane, isobutane, n-butane (10/50/40).A charge was prepared containing 98% by weight of dispersion A and 2% of a propellant consisting of a mixture of propane, isobutane, n-butane (10/50/40).

On a conservé la charge à température ambiante pendant 6 mois et on a vérifié la présence de niosomes par examen ultrastructural en microscopie électronique par la technique de la cryofracture. On a constaté que la charge renferme des niosomes ayant des diamètres compris entre 80 et 300 nm.The charge was kept at room temperature for 6 months and the presence of niosomes was verified by ultrastructural examination by electron microscopy using the cryofracture technique. It has been found that the charge contains niosomes having diameters between 80 and 300 nm.

EXEMPLE 7EXAMPLE 7

On a stocké pendant 8 mois les charges des exemples 4 et 5 et on a vérifié la présence de niosomes par le procédé décrit dans l' exemple 6. On a constaté la présence de nombreux niosomes ayant un diamètre compris entre 50 et 200 nm dans le cas de la charge de l'exemple 4 et de niosomes ayant un diamètre compris entre 150 et 400 nm dans le cas de la charge de l'exemple 5.The charges of Examples 4 and 5 were stored for 8 months and the presence of niosomes was verified by the method described in Example 6. The presence of numerous niosomes having a diameter between 50 and 200 nm was observed in the case of the charge of Example 4 and niosomes having a diameter between 150 and 400 nm in the case of the charge of Example 5.

EXEMPLE 8EXAMPLE 8

On a préparé une charge contenant en poids 70 % de dispersion B et 30 % d'un propulseur constitué d'un mélange butane-propane-isobutane-pentane (68,2/8/22/1,8). On a stocké cette charge pendant 8 mois à température ambiance et on a vérifié la présence de niosomes par le procédé décrit à l'exemple 6. On a constaté la présence d'un grand nombre de niosomes ayant un diamètre compris entre 200 et 300 nm.A charge was prepared containing by weight 70% of dispersion B and 30% of a propellant consisting of a butane-propane-isobutane-pentane mixture (68.2 / 8/22 / 1.8). This charge was stored for 8 months at room temperature and the presence of niosomes was verified by the method described in Example 6. A large number of niosomes having a diameter between 200 and 300 nm were observed. .

Claims (22)

1 - Procédé de préparation de mousses uti­lisables dans les domaines cosmétique et pharma­ceutique,dans lequel on charge dans une enceinte, qui résiste à la pression et qui est munie d'une valve, un produit cosmétique ou pharmaceutique fluide susceptible de former une mousse et un propulseur pressurisé, puis on ouvre la valve pour faire sortir le produit cosmétique ou phar­maceutique par détente du propulseur de façon à éjecter le produit cosmétique ou pharmaceutique sous forme de mousse, caractérisé par le fait que l'on utilise, en tant que composant du produit cos­métique ou pharmaceutique,une dispersion dans une solution aqueuse (D) d'une phase non-miscible à l'eau stabilisée par des niosomes constitués d'une ou plusieurs couches de composés lipidiques non-­ioniques encapsulant une phase aqueuse (E), cette dispersion constituant de 98 à 40% en poids de la charge de l'enceinte, le reste de la charge étant constitué de 2 à 60% en poids de propulseur.1 - Process for the preparation of foams which can be used in the cosmetic and pharmaceutical fields, in which a fluid or cosmetic product capable of forming a foam and a foam is loaded into a chamber, which resists pressure and which is provided with a valve. pressurized propellant, then the valve is opened to release the cosmetic or pharmaceutical product by expansion of the propellant so as to eject the cosmetic or pharmaceutical product in the form of foam, characterized in that one uses, as component of the product cosmetic or pharmaceutical, a dispersion in an aqueous solution (D) of a water-immiscible phase stabilized by niosomes consisting of one or more layers of nonionic lipid compounds encapsulating an aqueous phase (E), this dispersion constituting 98 to 40% by weight of the charge of the enclosure, the rest of the charge consisting of 2 to 60% by weight of propellant. 2 - Procédé selon la revendication 1, caractérisé par le fait que le propulseur est choisi dans le groupe formé par les hydrocarbures saturés ayant 3 ou 4 atomes de carbone, les hydrocarbures halogénés, et leurs mélanges.2 - Process according to claim 1, characterized in that the propellant is chosen from the group formed by saturated hydrocarbons having 3 or 4 carbon atoms, halogenated hydrocarbons, and their mixtures. 3 - Procédé selon l'une des revendications 1 ou 2, caractérisé par le fait que les lipides utilisés pour la fabrication des niosomes sont des amphiphiles non-ioniques d'origine naturelle ou synthétique comportant par molécule une ou plusieurs longue(s) chaîne(s) hydrocarbonée(s).3 - Method according to one of claims 1 or 2, characterized in that the lipids used for the manufacture of niosomes are nonionic amphiphiles of natural or synthetic origin comprising per molecule one or more long (s) chain ( s) hydrocarbon (s). 4 - Procédé selon l'une des revendications 1 à 3, caractérisé par le fait que les composés lipidiques non-ioniques sont choisis dans le groupe formé par :
- les éthers de polyglycérol, linéaires ou ramifiés de formules :
Figure imgb0004
n étant une valeur statistique moyenne comprise entre 2 et 6, R étant une chaîne aliphatique linéaire ou ramifiée, comprenant de 16 à 20 atomes de carbone ou le radical hydrocarboné d'un alcool de lanoline ;
- les éthers de polyglycérol linéaires ou ramifiés contenant deux chaînes grasses ;
- les esters de polyglycérol et d'acide gras à chaîne linéaire ;
- les stérols polyoxyéthylénés ;
- les glycolipides d'origine naturelle ou synthétique.
4 - Method according to one of claims 1 to 3, characterized in that the nonionic lipid compounds are chosen from the group formed by:
- polyglycerol ethers, linear or branched with formulas:
Figure imgb0004
not being an average statistical value between 2 and 6, R being a linear or branched aliphatic chain, comprising from 16 to 20 carbon atoms or the hydrocarbon radical of a lanolin alcohol;
- linear or branched polyglycerol ethers containing two fatty chains;
- esters of polyglycerol and of fatty acids with a straight chain;
- polyoxyethylenated sterols;
- glycolipids of natural or synthetic origin.
5 - Procédé selon l'une des revendications 1 à 4, caractérisé par le fait que l'on utilise de 0,5 à 25 % en poids d'amphiphile(s) non-ionique(s) par rapport au poids total de la dispersion de niosomes à obtenir.5 - Method according to one of claims 1 to 4, characterized in that one uses from 0.5 to 25% by weight of non-ionic amphiphile (s) relative to the total weight of the dispersion of niosomes to be obtained. 6 - Procédé selon l'une des revendications 1 à 5, caractérisé par le fait que l'on ajoute aux com­posés lipidiques formant les niosomes au moins un com­posé choisi dans le groupe formé par les alcools et diols à longue chaîne, les stérols, les amines à longue chaîne, les bis-hydroxyalkylamines, les amines grasses polyoxyéthylénées, les esters d'amino-alcools à longue chaîne, leurs sels et leurs dérivés ammonium quaternaires, les esters phosphoriques d'alcools gras, les alcoylsul­fates et les dérivés ioniques des stérols.6 - Method according to one of claims 1 to 5, characterized in that one adds to the lipid compounds forming the niosomes at least one compound chosen from the group formed by long chain alcohols and diols, sterols, long amines chain, bis-hydroxyalkylamines, polyoxyethylenated fatty amines, esters of long-chain amino alcohols, their salts and their quaternary ammonium derivatives, phosphoric esters of fatty alcohols, alkyl sulfates and ionic derivatives of sterols. 7 - Procédé selon l'une des revendications 1 à 6, caractérisé par le fait que l'on ajoute aux compo­sés lipidiques formant les niosomes au moins un lipopro­tide choisi parmi les dérivés mono- ou polyacylés d'amino­acides ou de polypeptides dans lesquels le restes acyle R-CO comporte une chaîne hydrocarbonée en C₁₃-C₁₉, au moins une des fonctions qui relie la chaîne polypepti­dique ou le reste d'amino-acide à la chaîne lipophile étant une fonction amide.7 - Method according to one of claims 1 to 6, characterized in that one adds to the lipid compounds forming the niosomes at least one lipoprotide chosen from mono- or polyacylated derivatives of amino acids or polypeptides in which the remains acyle R-CO comprises a C₁₃-C₁₉ hydrocarbon chain, at least one of the functions which links the polypeptide chain or the amino acid residue to the lipophilic chain being an amide function. 8 - Procédé selon la revendication 7, caractérisé par le fait que les lipoprotides sont choisis dans le groupe formé parmi le lipoaminoacide palmitoyl collagénique, l'acide dipalmitoyl-O-N-hydroxyprolinique et le linoléate d'hydroxyproline.8 - Method according to claim 7, characterized in that the lipoprotides are chosen from the group formed from lipoaminoacid palmitoyl collagen, dipalmitoyl-O-N-hydroxyprolinic acid and hydroxyproline linoleate. 9 - Procédé selon l'une des revendications 1 à 8, pour la préparation d'une mousse cosmétique, caractérisé par le fait que la phase aqueuse E encapsulée dans les niosomes contient au moins un produit pris dans le groupe formé par les humec­tants, tels que la glycérine, le sorbitol, le pentaérythritol, l'inositol, l'acide pyrrolidone carboxy­lique et ses sels, les hydrolysats d'élastine ; les agents de brunissage artificiel, tels que la dihydroxy-acétone, l'érythrulose, le glycéraldéhyde, les alpha-­dialdéhydes, tels que l'aldéhyde tartrique éventuel­lement associés à des colorants ; les agents anti-perspirants ; les déodorants ; les astringents ; les produits rafraîchissants, toniques, cicatri­sants, kératolytiques, dépilatoires ; les extraits de tissus animaux ou végétaux ; les eaux parfumées ; les colorants hydrosolubles ; les agents anti-­pelliculaires, les agents anti-solaires ; les agents anti-séborrhéiques ; les oxydants et les réducteurs.9 - Method according to one of claims 1 to 8, for the preparation of a cosmetic foam, characterized in that the aqueous phase E encapsulated in the niosomes contains at least one product taken from the group formed by humectants, such as glycerin, sorbitol, pentaerythritol, inositol, pyrrolidone carboxylic acid and its salts, elastin hydrolysates; artificial browning agents, such as dihydroxy acetone, erythrulose, glyceraldehyde, alpha-dialdehydes, such as tartaric aldehyde optionally combined with dyes; antiperspirants; deodorants; astringents; refreshing, toning, healing, keratolytic, depilatory products; extracts of animal or plant tissue; scented waters; water-soluble dyes; anti-dandruff agents, anti-sun agents; anti-seborrheic agents; oxidants and reducers. 10 - Procédé selon l'une des revendications 1 à 8, pour la préparation d'une mousse pharmaceu­tique, caractérisé par le fait que la phase aqueuse E encapsulée dans les niosomes contient un produit pris dans le groupe formé par les vitamines, les hormones, les enzymes, les vaccins, les anti-­inflammatoires, les antibiotiques, les bactéricides, les antifongiques, les agents anti-chute ou favorisant la repousse des cheveux et les rétinoïdes.10 - Method according to one of claims 1 to 8, for the preparation of a pharmaceutical foam, characterized in that the aqueous phase E encapsulated in the niosomes contains a product taken from the group formed by vitamins, hormones, enzymes, vaccines, anti-inflammatories, antibiotics, bactericides, antifungals, hair loss or hair growth promoting agents and retinoids. 11 - Procédé selon l'une des revendications 1 à 10, caractérisé par le fait que le liquide non-­miscible à l'eau dispersé dans la phase aqueuse D est une huile.11 - Method according to one of claims 1 to 10, characterized in that the water-immiscible liquid dispersed in the aqueous phase D is an oil. 12 - Procédé selon la revendication 11, caractérisé par le fait que l'huile est prise dans le groupe formé par les esters d'acide gras et de polyol, et les esters d'acide gras et d'alcool ramifié de formule R₄-COOR₅, formule dans laquelle R₄ représente le reste d'un acide gras supérieur comportant de 8 à 20 atomes de carbone et R₅ représente une chaîne hydrocarbonée ramifiée contenant de 3 à 20 atomes de carbone.12 - Process according to claim 11, characterized in that the oil is taken from the group formed by fatty acid and polyol esters, and fatty acid and branched alcohol esters of formula R₄-COOR₅ , formula in which R₄ represents the remainder of a higher fatty acid containing from 8 to 20 carbon atoms and R₅ represents a branched hydrocarbon chain containing from 3 to 20 carbon atoms. 13 - Procédé selon la revendication 12, caractérisé par le fait que l'huile est un ester d'aci­de gras et de polyol choisi dans le groupe formé par les huiles de tournesol, de maïs, de soja, de courge, de pépins de raisin, de cassis, de sésame, de macadamia, de bourrache et le tricaprocaprylate de glycérol.13 - Process according to claim 12, characterized in that the oil is a fatty acid and polyol ester chosen from the group formed by sunflower, corn, soybean, squash, grapeseed oils , blackcurrant, sesame, macadamia, borage and glycerol tricaprocaprylate. 14 - Procédé selon la revendication 12, carac­térisé par le fait que l'huile est un ester d'acide gras supérieur et d'alcool ramifié constitué par l'huile de Purcellin.14 - Process according to claim 12, characterized in that the oil is an acid ester higher fat and branched alcohol consisting of Purcellin oil. 15 - Procédé selon l'une des revendications 1 à 10, caractérisé ar le fait que le liquide non-­miscible à l'eau est un constituant pris dans le groupe formé par les hydrocarbures, les hydrocarbures halogénés, les polysiloxanes, les esters d'acide organique, les éthers et polyéthers et la perfluo­rotributylamine.15 - Method according to one of claims 1 to 10, characterized in that the liquid immiscible with water is a constituent taken from the group formed by hydrocarbons, halogenated hydrocarbons, polysiloxanes, esters of organic acid, ethers and polyethers and perfluorotributylamine. 16 - Procédé selon l'une des revendica­tions 1 à 15, caractérisé par le fait que la phase D contient un gélifiant.16 - Method according to one of claims 1 to 15, characterized in that phase D contains a gelling agent. 17 - Procédé selon la revendication 16, caractérisé par le fait que le gélifiant est choisi dans le groupe formé par les dérivés de la cellulose, les dérivés d'algue, les gommes natu­relles et leurs mélanges.17 - Process according to claim 16, characterized in that the gelling agent is chosen from the group formed by cellulose derivatives, algae derivatives, natural gums and their mixtures. 18 - Procédé selon l'une des revendications 1 à 17, caractérisé par le fait que la phase aqueuse D de dispersion des niosomes et/ou la phase aqueuse interne E des niosomes contient en solution au moins un polymère polyamide hydrosoluble ayant un poids moléculaire compris entre 1.000 et 200.000 dont la concentration est comprise entre 0,01 et 5% en poids par rapport au poids total de la dispersion distribuée sous forme de mousse.18 - Method according to one of claims 1 to 17, characterized in that the aqueous phase D of dispersion of the niosomes and / or the internal aqueous phase E of the niosomes contains in solution at least one water-soluble polyamide polymer having a molecular weight understood between 1,000 and 200,000 whose concentration is between 0.01 and 5% by weight relative to the total weight of the dispersion distributed in the form of foam. 19 - Procédé selon la revendication 18, caractérisé par le fait que le polymère polyamide est choisi dans le groupe formé par le polyacry­lamide, la poly-bêta-alanine, le poly(acide gluta­mique), la polytyrosine, la polylysine, et le poly(acide aspartique).19 - Process according to claim 18, characterized in that the polyamide polymer is chosen from the group formed by polyacrylamide, poly-beta-alanine, poly (glutamic acid), polytyrosine, polylysine, and poly ( aspartic acid). 20 - Procédé selon la revendication 19, caractérisé par le fait que le polymère polyamide est une protéine choisie dans le groupe formé par l'alpha-lactalbumine, le sérum albumine, les hydrolysats lactiques, les hydrolysats de collagène et les hydrolysats de gélatine.20 - Process according to claim 19, characterized in that the polyamide polymer is a protein chosen from the group formed by alpha-lactalbumin, serum albumin, lactic hydrolysates, collagen hydrolysates and gelatin hydrolysates. 21 - Procédé selon l'une des revendications 1 à 20, caractérisé par le fait que l'on ajoute le liquide non-miscible à l'eau à la phase aqueuse D contenant les niosomes et on soumet le mélange à une agitation intense avant de mélanger avec le propulseur sous pression.21 - Method according to one of claims 1 to 20, characterized in that the water-immiscible liquid is added to the aqueous phase D containing the niosomes and the mixture is subjected to intense stirring before mix with the pressurized propellant. 22 - Mousse obtenue selon l'une des revendi­cations 1 à 21.22 - Foam obtained according to one of claims 1 to 21.
EP90400307A 1989-02-09 1990-02-05 Process for producing foams for cosmetical and pharmaceutical use, and foams obtained by this process Expired - Lifetime EP0382619B1 (en)

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LU87449 1989-02-09

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GR900300137T1 (en) 1991-09-27
AU4917090A (en) 1990-08-16
ES2016788A4 (en) 1990-12-01
ATE75600T1 (en) 1992-05-15
DE382619T1 (en) 1990-11-29
CA2009607A1 (en) 1990-08-09
US5171577A (en) 1992-12-15
EP0382619B1 (en) 1992-05-06
DE69000085D1 (en) 1992-06-11
JPH0320214A (en) 1991-01-29
AU619077B2 (en) 1992-01-16
LU87449A1 (en) 1990-09-19
ES2016788T3 (en) 1993-06-16

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